Ketone-aldehyde-phenol-aldehyde potentially reactive resinous composition



Patented Apr. 7, 1953 UNITED PATENT OFFICE KE'EONE- Al;

POSITION Georg -e 'Kasivcsenan La- Mott, Fa assigncr to TheBcrasnccmpany, NeWYosmN. a cor- .po'ratio'n of New Jersey a 'I 'hepresent invention relates to *a 'netv r elclass of potentiallyreactiveregimes: col-npositions cssessing reslncidcharacteristics. The resinpidsof -the present invention: prepared by subjecting mixtures ei selected.-acetone-aldehyde and potentiall vreactivephenol ldehyde ia substantial iprovernentc closecllin application.:seriallNopeofls 3; 1 948, and.entitled Potentially-Reactive Coinpositions; Possessing. .Resin'oidCharacteristics? 13116 ob-jiect of the present invention is to prowide'a: nevv class. ofipoten'tially reactiveicornposi- .products that maybei'prepa-reid by} reacting "a ketone with ana aldehyde only: a handfulissu-itable for use in the present invention. Gilly-methyl ilsetones are'suitable for the preparation of the requisite condensation products.Further asthe number of-carbon atoms in the methyl ketonelincreases-,its reactivity with aldehydes diminishes and the resultant condensationproducts become less and less suitable for the purposes -01" thepresent-invention. When the radical combined to the methyl ketone.complex contains more 'thanlfourcarbon atoms,- it does not appear to befeasible to produce suitable condensation-products. "To be suitable,the'ketone-aldehyde condensation productmust be derived from. a methyl,ketone having the general. formula cllsdO R', .vvhereinR' represents analiphatic radical having from one tofour carbonatomsr "Only. aliphaticaldehydes containing Hve or "fewercarbon atomslen'd themselves towardthe production. of suitable ketone-aldehyde condensation products.Accordingly, 'the only I ketonealdehyde condensation productssuitableior use min the present" invention are those 'derive'dlfromtidehydes' having the general formuiain" cno, wherein represents amember selected from tl'ie fl cup "consisting of hydrogen and aliphaticradicals navir'ig frompnetc fcurcarbonatonis.

Ap lication Serial N o. 40165 its 22, T948,

(oi.- ace -4c) l'i jl ti 7 simple derivative, cannot be crystallized in"the 2 N ct all condensation products derived from the reaction betweeni the above-defined ketones. and. aldehydes are suitable for use inthepresentinvention. To be suitable, the ketone-aldehyde "condensationproducts must simultaneous-1y be fusible,-soluble, substantiallynon-resinous, substantially non volatile, and reactive.

By the term soluble I mean that the conde'nsation products must besoluble in one- 01' more of the following compounds or mixtures thereof:Water; aqueous acid solution, aqueous alkaline solution, methanol,ethanol, butancl,= acetone, ethyl methyl hetone, methylisobutylketone,

methyl acetate, ethyl acetate,butyl acetate, di-

oxane, formam'ide, acetamide, methyl-ether of ethylene glycol, ethyleneglycol, ethyl hexane: diol, concentrated formic acid, glacial aceticacid, furfural, tetra hydro furfural, tetra hydro furfurylalcohol-,Vphenol, cresol, 37% aqueous formaldehyde, ethylenechlorhydrin, propylene chlorhydrin, ethyl amine, ethylenediaminamonoethanolamine, diethanolamine, amino ethylethanol amine,morpholine, thiodiglycol, etc.

. While on the subjectof solubility? it should be pointed outthat thephenol aldehyde condensation products to be described later,- as=yzelloas the potentially l reactive compositions of the pres- .entinvention (prior to cure) are also soluble in the sense that they willdissolve in one or ---moreof theabovecompoundsor mixtures thereof. To besuitable for use-in the present invention: the: ketone=aldehydecondensation products -must besubstantially non-resinous; "In thisconnection it shouldbe pointed out that many ketone-alde'hyde"condensation products are res- THOUS in ifll 'elfa'ili'c'e Only ndthltWhlFS'ub jected to" rigorous analysis the products can be shown to benon-resinous by (l) a determination of their low molecularweig'ht(products of'low "molecularwei'ght eschew-resinous) (2) through ashowing that the compound, after the nec non-volatile can be uistill'edunder" appropriate conditions (in general-,i'resins cannot be distilledwithoutdecomposition) "or ('3) that the mate- "as; uch or in the remote.simple clenvacan" be crystallized '(resi'nsas s'u'cnfor their ordinarysense). Most ketone-aldel'l'ytle co'ii- "de ecation products arepossessed offacornplex "composition, comprising' a variety of relatedinat'erials. some instancesfthere may flv ry "small quantity crresiriousby-product material "wncsepresenceyin viewoftne' small quantityin which it may be present, is not unduly objectionable, but if asubstantial quantity of resinous material be present, the condensationproduct containing it cannot be used in the present process.

The ketone-aldehyde condensation products suitable for use in thepresent invention are, per se, not appreciably volatile and, owing totheir heat-sensitive nature, cannot, in general, be distilled inordinary equipment at atmospheric pressure Without decomposition. Thesubstantially non-volatile products may, however, be distilled unchangedvia the use of special high vacuum equipment (e. g., as in a molecularstill). In other instances, the substantially non-volatile products mayfirst be acylated and the resultant esters may then be distilled atelevated temperatures in appropriate equipment. In this connection it isemphasized that the fact that the usable ketone-aldehyde condensationproducts are substantially non-volatile should not be taken to mean thatthey are non-distillable. To all intents and purposes theketone-aldehyde condensation products suitable for use may be referredto as being substantially non-volatile. This restriction to the use ofthe ketone-aldehyde condensation products which are substantiallynon-volatile serves to exclude the readily vola- I tile condensationproducts (such as S-keto-butanol), which substances are eitherinoperative in the present process or lead to end products that areradically different in kind.

To be suitable for use in the present invention the ketone-aldehydecondensation product must be reactive in the sense that it can engage invariety of chemical reactions and, in a more specific sense, that it bepossessed of a specialized type of reactivity, to wit, that due to thepresence of a peculiar functionally reactive atomic grouping of unknownstructure which permits these compounds to undergo very readycondensation in the presence of a strong alkali. When a strong alkali,such as sodium hydroxide solution, is added to a ketone-aldehydecondensation product of the type under discussion, the same will, eitherimmediately or upon heating, undergo ready condensation, usually leadingto the formation of high molecular weight complexes or materials of theC stage resinous type (which latter are insoluble, infusible andsubstantially thermorigid). This unique type of reactivity is most'manifest in the ketone-aldehyde condensation products wherein theketone is acetone or the aldehyde is formaldehyde. The maximumreactivity is displayed by appropriate acetoneformaldehyde condensationproducts.

To be suitable for use in the present invention,

the ketone-aldehyde condensation product must be fusible. By restrictingthe condensation products to the fusible type there are ruled out themany infusible ketone-aldehyde condensation products which are eitherinoperative in the present process or lead to formation of end productswhich are radically different in kind.

Unsaturation in the aldehyde or the ketone employed in the making of theketone-aldehyde condensation products does not appear to materiallyaffect the characteristics associated with been found that materials inthe fluid, semifiuid or the solid state are equally effective. For

reasons of convenience, however, it is desirable to utilize the liquidcondensation products or, alternatively, in the instance of the solid ornear solid condensation products it is preferable to first thin themdown with an appropriate solvent so as to procure a readily pourableliquid. Fluid products are desirable because of the ease with which theymay be blended with the phenol-ah dehyde condensation products forpurposes of reaction, to yield the unique, distinctive and whollyunexpected compositions of the present invention.

Upon the basis of the above factual data the ketone-aldehydecondensation products suitable for use in the present invention may bedefined in terms of their derivation and chemical and physicalproperties as follows:

Ketone-aldehyde condensation products selected from the class consistingof the fusible, soluble, substantially non-resinous, substantiallynon-volatile and reactive condensation products produced by reactingtogether a ketone having the general formula CH3-CO-R, wherein Rrepresents an aliphatic radical having from one to four carbon atoms,and an aldehyde having the general formula R"CHO, wherein R" representsa member selected from the group consisting of hydrogen and aliphaticradicals having from one to four carbon atoms.

All ketone-aldehyde condensation products that fall within the frameworkof the above definition may be used in accordance with the presentinvention to yield the new, novel and unexpected potentially reactivecompositions of the present invention. All ketone-aldehyde condensationproducts that fall outside of the framework of the above definition areunsuited for use in the present invention either because they areinoperative or because they lead to the production of products radicallydifierent in kind from those of the present invention.

Ketone-aldehyde condensation products suitable for use in the presentinvention are best prepared by reacting a ketone with an aldehyde (bothas above defined) in the presence of an appropriate catalyst. It is notmy intention to here set forth any detailed procedure as to the methodof making ketone-aldehyde condensation products of the type indicated,but reference may be made to U. S. Patent No. 2,191,802 as setting forththe preparation of one type of ketone-aldehyde condensation productpreeminently suited for use in the present invention. The essence of themethod there disclosed resides in the fact that the reaction between theketone and the aldehyde is carried out in two separate and distinctstages, the reagents being first reacted in the presence of alkalisunder controlled reaction conditions to produce a homogeneous andfusible intermediate product, after which an acid catalyst is added,said intermediate product being further reacted under acid conditions.Of the various condensation products therein described, the materialreferred to as standard AFR is ideally suited for use in the presentinvention. In connection with the standard AFR, it is interesting tonote that in spite of its resinous appearance, it has been found thatthis product is essentially non-resinous in character, is possessed of alow molecular weight, can be distilled in a molecular still and canreadily be acetylated to an acetate which is readily distillable andcrystallizable.

I have thus far discussed the nature only of the suitableketone-aldehyde condensation products. Of equal importance is the natureof the phenol-aldehyde condensation products that are awesome area in;eon uncuen with the above identified f lrettm'eealdehyde condensation-products 1. to produde the potentially reactive'compositiohs of thepresent invention.- i r For purposes of nuence of reasonable heat-theyw'ill n'ot become conveeted-te Y the intusible inso-Iulele' and-ithermorig id states 'Novolaks -are u'sually prepared 1 :by reacting apnenbrwuh an aldehyde iii-the proportion of one mole of phenol'to oneori'slightly'iless than one" mole of ald'ehyde, generally "in 1v the*presenee #of a catalyst. 'They 'oannotof themsaves-ts eonveitedto 1 theinfusible; insoluble and ermo-rig'idstate. 1 However, through the agency"of appropriate 'cross linking agents, acommonly referr'e'd -to ascuring or hard'ening agents, as typi fied by materialcon-tainingre'activer methylene eroups ('e. g ithexamethylenetetra-r'nine) it is "possible to procure qipotentially'ireactive composins 'whioh, whenTsubjected "to a proper timetemperatureschedule,are' convertible to the" infusible, insoluble, and thermoarigid so-fcal-led C I' st'ate. I

Phenol-aldehyde condensation products of the novolak "class areessentially unsuited. for use in "the pursuit i'of the presentinvention. Novolak resins are not 'possessedxof the. necessary. 'func--'tional attriloutes F that are d'ir'ectly rconce'rned in -theproduction 'of the -potentially reactive: com- "hosi tions of thepresent invention.

Phenol-aldehyde condensation'products of the no'n novolak' type are 1commonly referred to as be'i-ng' of the potentially reactive type. andthat i'ierrn'inologywill be used in this specification. The .ich'ief"attribute of the .phenol aldehyde condensa- -tionf products of thepotentially reactivetype is the factthat upon long "standing :atordinary temperatures, or rapidly under the influence-of wheat, theywill undergo reaction :and become con- ;verted to -the infusible,insoluble and thermon'igidistate (theso-calleol 0. stage). It is to beobserved that-resins of the potentially reactive type, incontra-distinction to resins of the novolak type are convertible to theC! stage by merely treating them; without the. necessity of having toadd a co -reactant or cross-linking agent. Potentially reactive resinsare frequently referred to as""single stage resins. :Potentiallyreactive phenolic resins are"preparedbyreacting a phenol "'Tv'vith aTquantity of aldehydewhich, if" the reactionlae*cai'ried'to'completion,is capable of yield- "ing'thehltimate infu'sible, insolubleandthermorigi'd form 'of'resin. 'Thisgenera1ly calls for a quantity ofaldehyde that is in substantial molar 'fexce'ss 'of thequantityofphenol' employed. The

typepfcatalyst'used depends upon the nature of the reaotantsemployd."Intne'instance of phenol 'f'and formaldehyde, it is customaryto'utilizean jal kaline catalyst, e. 'g., sodium" hydroxide.

stu y and utility it iscustomary to divide phenol aldehydecondensation-prodsation :Pproduct depend upon '1 thetnaturezof thephenol, -aldehyde and the-catalyst employed Well upon whether or not adiluent is used carrying outtherea'ction. "Itis also influenced by "thetime-temperatureschedule employed. ZThe preferred phenols. for theproduction of potenti-ally reactive phenol-aldehyde condensationproducts suitable for use in the present invention are phenol, 1 meta"substituted libel-101s (sudh as 'xneta-oresol) 3 5substitutedphenols1e. g3 '5 f -ii'y-lenol) yresor'c'inol and' phoroeluoinoh 1Although anyone of several aldehydes' may "be utilized fortheprodllilti'bvii of "potentially reactive resins- Sllit- "abl'e for'use inf' the j-pursuitof the present' invention,"I believethat'rormaldehyde and, in some mstances; "'glyo'xal are the preferredaldehydes. Paraiormaloehyde maybe used in'lieu of -formal- Cl'ehydeLPurified non-resinous 'phenol aldehy'de condensation "products such" asphenol d n'd tn-alcohol are preeminently' suited ionuse i jpresent'invention.

Onlyphenol-aldehyde'condensatlomproducts of Ijtheipotentially"reactivetypeare suitable for use "inthe pi1T'suit of'the'pre'sent invention. All -"otl ier types "of phenoPaldehyde"condensation "productsare essentiallytunsuited.

''rn j'precise"physics" and chemical" properties orapotentiallyreactivephenohaldehyde conden-Potentiallyreaotivephenol-aldehydecondensa- 'tion products may beproduced ineither the s'olid or liquid state. The liquidcompositions-usually i. owe their' fluidity to the'prese'nce ofafiui'd'marenal or solvent (e. g., waten' f-ree phenol, I alka lineaqueous solutions, 'aleohol, acetone, isoproptthol, methanol, or-aqueous solutions of' the "aforementioned"'=alcohols9 For-thei Tpurposes afif the present invention "the potentially i'eactive "phenol-aldehyde condensation-product may be in either the liquidor solid-state. "For reasons of convenience it is desirable to-util'ize thecondensation product in the form of a' solution or 'as a liquid resin. 7l

' In :my copending= application, serl -No.'- 3073 3, previously referredto,1it isdisclosedthat resirioid mixtures ofthe abovespecifiedketonealdehyde and potentially reactive 'phenol-aldehydecondensatiorr'produ'cts constitute an improved "composition of matterpossessing desirableproperties and' that in particular such mixtureswilliresinify much niorequick-ly than either of 'theirwompone'ntsstanding alone to' forin'insoluble and fusible thermoset compositionspossessed of new and unusual properties. In a'ddition, the curedproducts of the mixtures of-the copenclin'g application exhibit"great-physical "strength' and' -w ater 'and' chemicaI resistance,thestrength'heing ma- "teria'lly greater than "the'strength' or 'thecured "productsof "either of the "components "standing alone, and thewater and chemicar'resistance =being either equal to 'orsuperior'tothoseof the "cured products'of the components of 'the mixture standingalone. 'It is"'pointed-out in -the aforesaid application that the curedproduct de- "rived from said mixture apparently consists ot "threeniajor constituents,- one being curedaphenol aldehyde resinouscondensate, "another be- "ing a ouredketone aldehydecondensationproduct; and the third and-largerportion of th'e' vvhole consisting er acured-product resultingiromthe 1 reaction between 'ketone-aldehyde andpotentially reactive*phenol aldehyde condensationprodu'cts. Inconsidering the present invention,- it must be clearly kept in mind thatthe-resinoid products-of the copending application aramerely mechanicalmixtures of the ketone aldehyde-and potentially" reactive phenolaldehy'decondensation'produ'cts, and that no chemical comhinationbetween those two components takes placeprior to the time that they aresubjected tothe cu'r- *in'g step 'andcarried through to form insoluble"and'infusihlecurediprodu'cts.

covery that if the potentially reactive mixtures of the afore-describedinvention are subjected to conditions of controlled resinifioation,short of the point of gelation, the resultant products are endowed withall the novel and distinctive attributes associated with the potentiallyreactive mixtures of the afore-described invention, with the importantdifierence that all of the aforesaid attributes are now greatlyaccentuated. In general, the further the reaction is carried, short ofthe gel point, the better the product. Thus,

-while properly formulated potentially reactive mixtures of the priorinvention can be made to cure about three times as fast as the componententities per se that entered into the mixture, the potentially reactivereaction products of the present invention may cure fully three times asfast again or about ten times as rapidly as the original componententities. Further, comparing the reaction products to their mixtures, itis found that the former yield more homogeneous products--a much largerproportion of the ultimate cured products consists of the inter-reactionproducts in the cured state rather than the separated componentsper sein a cured state. It has also been found that the reaction mixtureyields products of increased mechanical strength and greater uniformityas compared to the cured products derived from the afore-describedpotentially reactive mixtures.

The manner in which these products are produced is relatively simple.The first step is to secure a homogeneous mixture of the twocondensation products. The resultant mixture in eifect constitutes apotentially reactive composition of the type disclosed in copendingapplication, Serial No. 30,733 previously referred to. The mixture isthen subjected to controlled resinification by subjecting thepotentially reactive mixture to a predetermined time-temperatureschedule.

For practical reasons, so that the reaction may be completed within areasonable period of time via the use of conveniently obtainabletemperatures, the use of an alkaline catalyst is preferable, but notnecessary. As catalysts one may employ any compound or combination ofcompounds calculated to maintain the pH, during the processing, towithin a desired predetermined range, preferably between 7 and 9. Theuse of a pH above 9 is permissible but the reaction becomes more erraticand difiicult to control. The use of a pH below 7 is permissible but thereaction becomes unduly prolonged unless higher than usual temperaturesare employed. The preferred catalysts are similar to those used toeffect catalysis of the completed product for the purpose of curing thesame except that the strongly alkaline compounds of the polyvalentmetals are not recommended here since they tend to cause prematuregelling. Such cure catalysts are described in a subsequent portion ofthis specification. For most applications it is found that sodiumhydroxide, which is both economical and readily available, can be usedvery advantageously.

The purpose of the processin is to effect a reaction between theketone-aldehyde and the potentially reactive phenol-aldehydecondensation products. The speed of the reaction is influenced by (l)the nature of the condensation product employed; (2) the ratio of thereactants; (3) the relative concentration of the reactants (in virtuallyall practical systems some inert solvent or diluent is present); (4) thehydrogen ionconcentration (this is largely governed by the amount andtype of alkaline catalyst employed) and .the temperature at which thereaction is carried out (operation under pressure may be resorted to ininstances where it is desired to operate at temperatures above theboiling points of the more gel point. rate is too slow, then obviouseconomic consideravolatile ingredients present) As already inditionsintervene. From the standpoint of commercial operation, it has beenfound advantageous to carry out the reaction under conditions such thatit can be carried out in between about onehalf and about four hours.

For the purpose of moderating the reaction and enabling the operator todetermine the end point without too much difiiculty, it has been founddesirable to carry out the reaction in the presence of a more or lessinert diluent or solvent. A certain amount of solvent is usuallycontained in the original condensation products, Where this amount issubstantial, it is unnecessary to add any additional diluent. In manyinstances, however, it will be found necessary to add an additionalquantity of solvent so as to dilute the concentration to a desirablelevel. For this purpose it will be found that one or more of thecompounds or mixtures thereof that have been previously listed as amongthe potential solvents for ketonealdehyde condensation products may beemployed for this purpose. It is generally desirable to use a volatilesolvent which can readily be distilled ofi or which will evaporate whenthe finished product is put to use. Among the preferred solvents aremethanol, ethanol, acetone, ethylene glycol, and its methyl and ethylethers. It is usually necessary to include a certain amount of waterwhich functions in the role of coupling medium, No more solvent thannecessary should be employed.

In a properly composed system all the ingredients entering into thereacting mass are usually in a state of mutual solution. Exceptions tothis rule occur in the instance where substantially insoluble modifyinagents, e. g., copper oxide, zinc oxide, etc. are included in thecharge. It has been determined that satisfactory commercial 'operationmay be achieved when the actual solids content of the reacting massranges between 50 and When the solids content exceeds 80%, theconcentration of reactive components is rather high and difiiculty isexperienced in carrying out the reaction without premature gellationsetting in. When the concentration of the reactive condensation productsis less than 50% an unneeded large quantity of solvent is present andthe reaction is usually unduly drawn out,

In the instance where the two condensation products to be reactedtogether are nominally more or less incompatible with one another, twoalternatives are open, viz. (1) one may effect solution through the useof a coupling medium or solvent, or (2) one may produce a dispersion oremulsion by any one of several recognized methods. The new entity thatcomes into being as a result of the reaction between the two types ofcondensation products may or may not be compatible with one or both ofits progenitors.

The reaction between the ketone-aldehyde and Meme 9?therpotentialiygreactive.phenolealdehydeconderre sationproductszoccursxsatwaniappreciabler rate at temperatures :above about120? F.;,,.and virtually allioif; thegmorezuseful landmoresireactiveresinoids ofrthe: .inventionare: adv antagerrasly pro-- ducedhyoperatinagwithin. the temperature range In; instances where appreciable:amounts of waterinrrother .volatile-solvents. are present, the presenceof these materialslzendows.the.charge with a more or less; fixedlbeilingor reflux 'tem perature. At agiven pressure, e. g., atmospheric, theboilingor'refiux temperature-of the reacting mass obviously sets'theupper temperature-limit. Because of this" circumstance, it ispossible through the choice ofiappropriate quantities of proper;diluents; to" automatically the upper temperaturelimit. Itth-us becomesfeasible to merely heat the reacting charge-to the 'refiuntemperature(which usually'changes but "slightly duringgthecourse of the'run) "andto then-maintain a gentle reflux" throughout" the reaction period,thereby maintaining the temperature at-a prede terminedfpoint throughoutthe course" of the reactiorrby utilizing'an appropriate concentrationofiselected solvents in the charge; The use of a solventfor: this.purposerat thesametime serves asa diluent'that moderatest'hereactlonand thus permits it to'run" a smoothercourse d'evoidoi erratic andcriticalihehayiorzu V Thereaction. shouldbe continued just short ofthehel points O'noeone..hasestablished the time required. .to reach: the,gel point (for a charge of elven composition in. a given: piece orapparatus) itii is. a.re1ativ.ely simple. matter to .stopgtheproc- Iessingiiust shorter. that. point; In order toprcride. someleeway. and.to avoid. the possibility of a. batch being. carried too. far; (oncethe material has gelledfitis virtually useless-forthe majority of.commercial, applications) it. isrecommended tostopgthe...reactionshort.oi'jthe .gel point by a. reasonableperiodofutimeu. Itthe gellpoint isreached in,,say,.threei hours. time.(during. which time the I composition is...maintained' atthereflux.tempera:- ture) .the.reactionlmay. lea-stopped. aiterqabout two.andlone-halthonrs. In-..commercial. practice itthasrbeenfoundadyantageous todeterminethe gettnnebycarrying out.asma-llrun'inthelaboras toryunder controlled'conditions... 3

Up.on;l..the...basis.o the. aboize. information. the preferred...procedure for. the production. of.- f the resinQidsotthe.present...invention is. as. follows Selected ketone aldehyd'e andpotentially, reactive. phenolealdehyde. condensation. products. arestirred together. to produce a. homogeneous. mixture... Where necessary;there is added to the mixture .a. moderate. quantity; of an appropriatediluentsuch as. ethyl alcohol; isopropyl alcohol, et r fiche-glycol orits mono-methyl. ether. A; small quantity of catalyst, such as a4/normal, iaque-s ousvsodium hydroxide solution, is slow-1y stirredin... Themixtureis}thenheated to the. reflux tem-jperaturei. Thamixtureisrefluxedifbr. a? period ofe time reasonably, short .oi.the..predetermined gel point. When the=reactiontime is up, thereactionisstopped by. cooling- .thereaction product.

time. between: the time; when thereactionisstopped and when thetemperature hasrdropped tothat of the ambient surroundings. Plasticizersorother materials may rbe incorporated to modify or: accentuate. certainattributes.

The following examples. are. illustrative. of the above disclosures:

Example I pounds). The above condensation products. were stirred.together until homogeneous mixturerree suited. As reactionmoderatorthere were added 2520 mil of. ethyl alcohol. Aftersolution acata- IystWQQ mil or i/normal aqueous sodiumhydroxide w solution) was,slowly introduced. with continuous stirring. The: charge was :heatedtothe reflux temperature (temperature of reacting mass approximately 198'F.)'. A- small vtestrun in a laboratory (in. glassware) indicated thatthe gel. point at this temperature occurred. in about an. hour and-1a.halt. The reacting; mass was maintainedat therefiux. temperature for aperiod ot ahout one hour (i. e., one-halfhour'short oi the gel. point)Theheat." was. then :turned off and cooling water applieduto bringthe-1product down to room temperature. The reaction product was in theform of a thick; amber colored honeylikeLmassr Itixpossessed .a: nominalshelf life at ordmarytemperatures, but could. be stored under 7refrigeration; for" prolonged periods of time. When1..appropriately;catalyzed (e. g:; ,via l/norg mal. NaOI-I) the: product cured veryrapidly-at temperatures of 220 F. The rateof cure was approximately;three-times that of the same mixtime prior: to reaction-,; or, stated.another way, the product curedin approximately one-tenth the timerequired for the curing of either of the orieginal condensation productsthat entered into its making. The productwa's miscible with ethyleneglycol .in;all='proportions-,: .but was. only partially miscible: with.acetone, methanol, ethyl. alcohol,

isopropanoL. orwater;:. The-product hadiia. high tolerance-.foraqueous'solventblends; .e. an, .aquee ous acetone. c

' Example II A' product-identical with. that of EXampletII was firstprepared. Aftertheadditionof the 2 ethyl-hexane-diol-l-3," the mass'wascooledto approximately L'F. Then, with continuous stirring... therewere. slowly, added 34.9 pounds otaqueous'acetone (one part .by weightoface-. tone to. three parts by weight. of water) as a sol-- vent. Theresultant solution, while still warm, wasstrained through cloth toremove scale, etc.

The product of this The yield was approximately 134.5 pounds of a thinamber, honey-colored syrup. The product conformed to the followingspecifications: standard solids 49.5%; low temperature solids 63.3%;specific gravity 1.148 C.); specific viscosity 200-400 centipoises; pH7.6.

Example IV Ketone-aldehyde and potentially reactive phenol-aldehydecondensation products, qualitatively and quantitatively similar to thoseof Example I, were stirred together. Then 2520 mil of the monomethylether of ethylene glycol were introduced. After stirring a few minutes700 mil of a 4/normal solution of sodium hydroxide were slowly added.The mass was then heated and maintained at approximately 200 F. for aperiod of 1 /2 hours (approximately hour short of the gel point). Afterthe reacted mixture was cooled to about 165. F. there was added asolution comprising 8.75 pounds of the monomethyl ether of ethyleneglycol and 8.75 pounds of ethylene glycol. The mixture was stirred toassure uniformity. The yield was approximately 110.5 pounds while thespecifications were as follows: low temperature solids 83.5%; standardsolids 60%; specific gravity 1.223 (25 C.); specific viscosity 8250centipoises; pH 7.3. The product of this example was quite similar tothat of above Example III from which it differed in that the more readyvolatiles of the latter were replaced with less volatile compounds so asto adapt the composition to applications where lower orders ofvolatility are called for.

Example V A potentially reactive composition identical with that ofabove Example IV was first prepared. To 100 parts by weight of theproduct of Example IV there were added 27.5 parts by Example VI To 56.9pounds of a ketone-aldehyde condensation product (standard AFR as per U.S. Patent 2,191,802) there were added 32 pounds of a potentiallyreactive phenol-aldehyde condensation product (prepared by reacting 8pounds phenol plus 8 pounds of meta cresol with 25 pounds of it'laqueous formaldehyde in the presence of an alkaline catalyst andconcentrating to a net weight of 33 pounds). The above condensationproducts were stirred together until a homogeneous mixture resulted.Then 2 litre of the monomethyl ether of ethylene glycol were added.After solution the catalyst (500 mil of 4/normal NaOH) was slowlyintroduced with continuous stirring. The charge was heated to the refluxand kept there for a period of one hour (about hour short of the gelpoint). The reacted mass was then cooled to 180 F. and diluted with amixture of ethylene glycol and its monoethyl :ether. The resultant lightamber colored product was possessed of a medium viscosity.

Example VII To 60 pounds of a ketone-aldehyde condensation product(prepared by reacting acetone with about 4.5 moles of formaldehyde inthe presence of potassium carbonate as catalyst and then concentratingby evaporating off the ready volatiles) 12 there were added 35 parts byweight of a potentially reactive phenol-aldehyde condensation product(prepared by reacting 1 mol of phenol in the presence of 2 moles ofbutylaldehyde using sodium hydroxide as catalyst). The condensationproducts were stirred together until a homogeneous mixture resulted. Themixture was then heated to reflux and maintained there for a period ofapproximately two hours (about threequarters of an hour short of the gelpoint). The resultant viscous material cured less rapidly than theproducts of'the foregoing examples, but nevertheless cured two to threetimes as rapidly as the original mixture prior to reaction. The butyricodor associated with this product limits its utility.

Example VIII One hundred pounds of an ethyl methyl ketone-formaldehydecondensation product (prepared after the manner outlined in U. S. Patent2,191,802) were mixed with 30 pounds of a potentially reactivephenol-formaldehyde condensation product of the type used in Example I.A litre of anhydrous ethyl alcohol was added along with 250 mil of anS/normal sodium hydroxide solution. After stirring until a homogeneousmixture resulted, the mass was heated to reflux and kept there for aperiod of approximately 3 /2 hours (about an hour short of the gelpoint). The resultant product was somewhat similar to that of Example Iexcept in that it cured at a somewhat slower rate, possessed a lowertolerance for water but a higher tolerance for organic compoundscontaining hydrophylic groups.

Example IX One hundred pounds of a ketone-aldehyde condensation product(prepared by reacting methyl isobutyl ketone with formaldehyde after themanner outlined in U. S. Patent 2,191,802) were mixed with 15 pounds ofa potentially reactive phenol-formaldehyde condensation product(prepared by reacting 1 mol of phenol with 1.75 mols of aqueousformaldehyde in the presence of sodium hydroxide). Two pounds of sodiumhydroxide dissolved in 6 pounds of water were then slowly introducedwhile the mass was being vigorously stirred. The material was heated toreflux and kept there for a period of about three hours. The resultantviscous product had a very low tolerance for water but was quite solublein ethyl alcohol, ethyl methyl ketone and the monomethyl ether ofethylene glycol. While much slower curing than the products of the priorexamples this material was well suited for use as a bonding agent inconjunction with appropriate fillers in applications where oven curingis feasible.

It is to be observed that in the pursuit of the present invention theketone-aldehyde and the potentially reactive phenol-aldehydecondensation products are reacted together short of the gel point. Ifthe reaction is carried to or beyond the point of gelation the resultantproduct is possessed of little intrinsic worth for the applications forwhich the compositions of the present invention are intended, since theresultant prod ucts wouldthen become substantially infusible andinsoluble. In marked contrast thereto, when the reaction is run short ofthe gel point, the resultant products are fusible and soluble. In viewof the fact that the compositions of the present invention arepotentially reactive, i. e., are heath-ardening in character in thatthey change from the soluble and fusible state to the insoluble andinfusible solid state on heating, the products are 'undertheir ownweight.

'aipptopriately-p termed? resinoidsf term resihotds,asusedthnoughontzthetpresenttpecie fication" elai-ms; vhasureferencetoarsolnble and 1 3 hfusiblewresinous-entity which; uponythe; applicae;tion oofj"heat-under: appropriate conditions; lee-g comes -oonve1tted torthet insoluble: infusible;

solidstate. I t I "The resineids: of -the presei'nn' iitxventidnsirange;in? consistency: item water thin fluids? toe eretremely viscous masses:that? Willis barely: flow; Thee: consistency:- is; largely contrelled Ithe quantity" and itype :of selvent -that is presentiduring:thereactions or added thereafteri it The-resinoidsv areflsclublef'inthesense'th'at they-will 'dissol vein onezcnmore; -or*l'ncombinations;oti' the solvents 'thathave talc-.

ready 'b'een'" enumerated connection with solubility of theketone-aldehyde condensation products usable in thepresent-invention;Water cannot b'eeempl'oyed as: they sole: solvent hutf it 2G; has'beenfouncithat 'aqueous solutions ot"acetone;' V

methanol; ethanol; or' -isopropanol ior mixtuices;

thereof-j often: give-*- excellent results- WheIYeJa less readily:volatile- 'solventis required; materials:

such as ethylene glycol; diethylne glyoot on the colhave pr'ovenvery'-satisfactory;

' The-prodiictswf "the present "nvention'inay bevariously-modifiedthroughtheinelusidn of othen materials: Depending uponthe=circnmstances the .modifying agents may he incorporated" either"during" the processing operation or: they ma be added" to *the prodiictafter reactien.

At' the ti me of"curing-there is adddtc: the" potentially-reactivecompositions of the present;

invention astrongly alkaline cataliist', the ameiint and type of whichdepends upon the natureof 25: monomethyl ormonoethyl ethers ofethyle'neglya theapplication: The strongee-the-alkaline ma V terial themore potent its '-catalyticproperties."

- The? 'greaterthe quantity 'of catalyst that-is;

' ad'ded; the: fasten the cure-fi Thealkaline: cataa lystsinayybelongfto any? one; ofseveral classes. Ti'l'e hydfexides of cesium;rubidium; potassium,

sodium andlithum; preferably-in!theferm ofaqueous "solutions; areadmirablysuit'ed t'octhispurpose: Thehydr'oxides of barium, strontinm flandficalium; are not particularly :recommendedowingztopeculiar sidereactions that occur when these materi'als. area utilizedi as. sole wecatalystr Stronglyalkaline water-soluble compounds of the alltati:metals, such xasfialkali: metalizincate;

plumhjate; alum-mates etc; aregexcellent catalysts; 1

althcugh" in" most: instances; in" orden :"tc prevent premature:gelling;- iti isc advisable. to HIiXIJZSllChTL alkali metalii compoundwith:.alkalt= metat. 1 hydrlcxidz Tlig-l stronger -organiesamines;partioue lai -1y polyamines'gofitheatype;offzethylenediainine;

diethylenetriamina ,triethylenetetramine;; and tetraethylenei pentamineiate: very; suitable: asi catalysts; thongh'itheyrare not-as potentasthe;

alkali; metal: hydroxides, and suffer fromrthe dis! advantage; in that;owing to: their poly functional ch'aracter;; theyhave a. tendencytowarclp premature; gelling;; The organicv ammonium bases'such astetraethanol amnmniumihydroxideand. benzylw trimethyl-u ammoniumhydroxide; 'iunntionas potent'catalysts,andhave-the advan ta-ge; forscmeaapplieationsgafterthey haveheen heatedduringxtheprocessntcuretheyadegenerate; intmmilder alkaline 3 materials; For:pnrposesvot convenience we come: 170:? look: unoni an;

dehydtatwtlieepizodnctssofjtheeptesent intention theytinvariablyrpass:into; asjelil or: semi-nubbery; state; which; circumstance pneohzdes thepresume ment. of these 1.- products in; the. soluble; Lfusible;

andcg'rindably hard; solidoistatew Compositions, which o contain at highpercentage of: phenol;-- aldehyde condensation; products: be; 103F061-essedz itontheitgrindalcly hand, solid state but: tunfortunatelmtsuchcompositions; owingtov thetlow 1 percentage: of, ketone-aldehysde'.condensation attributes; associated, with. thE PlCOdLlQtS, ot thepresent invention;are:manifestedntc-ma.smaximmm degreeetl y whenacetone; israeccmponentiofithe ketoneealdehydecendensation product;(2)-.-when termalclehyde is a componentl of: the; ketenealdehydecondensatieni product; 433-;- wlrien phenol; metacresol; 3,5:xylenohortresorcinol a component :of the =phenol-aldehydesoondensation productandzUl-t whenqformaldehyder on gtyoxals isaaycomppnent of.thevphenol-aldehyde cendenV- satiore. product. i It appears-.-that'-f,0r; most putsposessthe: :hest mesults-ares procured whenappree pit-lately; p epat'ed: acetone-@fotmaldchyde condemsationproducts. areemixedt with: potentially re,-

aetivephenol-fo1:maldehyde-rcondensation ppode nets: The;:;physiealand;-chemical-,.-attnibutes; line cluding the -shelfiliteenwhiehemaywrangebetween.

threamonths anclttwo years ase naturally gneatlys' influenced: I byethe; extent to' wh-ich :theereaction between: the :condensation pneduetsshes sheen- G3) i 'riedt: Aswalready indicated;- -the-eloserthe-resaction is :catried; to .the gel: point; the-.-hettei= rthe:produets :fromz,thesstandpoint of. speedinesss oft cune -etci, thoughatia?corresponding-sacrifiee:in

the shelfslitea l Flo-1: reasonsnot fully understood.itihassbeenobserved thatrpreductsemade outof thficfl-CQtQDB' formaldehyde;condensation 7 products; produced after; the manner. disclosed in UK.Patent 2,191,802: appeals vtevloe,=-snperionto andadifi-enent from;thosee-de aivede fnom;acetoneetormaldehydel condensationpnoductssproduced.metelygviatatkalt environments.

Fonthe pur-posessnf --the.present ;-inventien. -thecatalysiswithout.subsequent reaction: insan acid:

'- ratiomfg the phenel-aldehycle to-rtheketeneealdeehydeecondensation;graduate*thatare-yeacted toegethen: may lcover, at wide range; 7 It: haweiound.

Y that in order-that the:compositions;afiterireac tien; manifest-toz-ajsubstantial degree the annex:

pected-,. novel and: highly: desirable functional Eat; tributes Jwi-th.whichuthel resinoidseot the L 'pites'ent inventions are; endowed, itiS-IIBCQSSBJEY- that the phenolealdehyde condensation precl-uot. (inteisms;

ofi'solids content onaweighthasis) be. ptesentfto,

the-extentzot notitless than. 5%. upon-the; come! aqueous 47=normal1spdiumihydroxide solution as I the:..-standard catalysti.

1 The? resinoidsi: o the present invention: are

usuallyunhwmore 'l'ess fluidtstatez', It. is a- I peculian: teem-that?hem an: .attempt.;.-is -:made ate;

the=extenttof;between.-10=and:30 uponethe come a bined weightsnat the tncondensation g zoolncts hinectmetehts ot the twozcondensation,produtits.

; The uniquewand; distinctive attributes associated with, r-thepeed-nets of, the tpresentinventiom are manifested :intthetlargestdegree: when .thephe: nol-aldeh'yde condensation pzoctuctwisrpresent lto.

When the phenol-aldehyde condensation product is present to an extent inexcess of 50% upon the combined weights of the two condensationproducts, then the attributes of the ultimate product partake more andmore of those associated with an ordinary modified phenol-aldehydecondensation product. When the concentration of the phenol-aldehydecondensation product exceeds 90% upon the combined weights of the twocondensation products, then the distinctive attributes manifested by theresinoids of the present invention are no longer readily discernible.The fact that the maximum showing of the distinctive attributes of thepresent products is manifested when the ketone-aldehyde condensationproduct is present to the extent or between 50 and 95% (best between 70and 90) upon the combined weights of the two condensation productsindicates clearly that the ketonealdehyde condensation product shouldcomprise the major portion of the whole.

When the resinoids of the present invention are permitted to cure in theform of films or thin sections exposed to the atmosphere and subjectedto a controlled time-temperature curing schedule, the resultant productsare dense, clear and homogeneous. When the resinoids of the presentinvention are subjected to curing conditions in thick cross sections,under circumstances where the opportunity for the escape of ready erallycontain a substantial quantity of' inert fluids of one type or another,this phenomenon is quite general. Under appropriate conditions oicatalysis and a carefully controlled time-temperature schedule, it ispossible so to cure masses of the potential reactive compositions of thepresent invention that they will yield hard, strong, dense, curedproducts, but the cured prodnot will normally be in the form of small,more or less broken up, fragments, owing to the circumstance that as thecure progresses the shrinkage is so great that the resultant stressesand strains within the material caused the same to split and fracture.Under appropriate conditions of catalysis and via the use of a very slowtime-temperature schedule, it is possible to cure the resinoids of thepresent invention so that the mass during'the process of cure does notbreak up into small pieces, but under these conditions the resultantproduct will be extremely microporous in character. For certainapplications such microporosity is not objectionable and may indeed be ahighly sought after attribute.

The resinoids of the present invention may be variously modified so asto suit them to specific applications. For example, for some purposesthere is desired a product which, in the ultimate cured. form, ispossessed of a low resistance toward water, i. e., is waterdisintegratible. It has been discovered that such compositions arereadily procured when there is added to the po-- tentially reactiveproducts a water-soluble material such as ethyleneglycol,diethylene-glycol, glycerine, triethanolamine, sugar, etc.

For some applications it may be desirable to extend the resinoids of thepresent invention. This can readily be. accomplished through theaddition of materials such as water-soluble compound-s of lignin (e. g.,lignin-sulfonic acid which is produced on a large scale as a by-productin the manufacture of kraft paper). Up to 50% of such lignin-containingmaterial may be added to the more water-soluble compositions of thepresent invention to yield ultimate cured articles of excellentstrength.

The resinoids of the present invention constitute distinct chemicalentities having different properties, both chemical and physical, fromthose substances not coming within the scope of this, application.Differentiation ha already been made between the substances of thepresent invention and those of my application, Serial No. 30,733. Itshould also be noted that the products of the present invention differfrom those resulting from the reaction between a phenol'and a ketonealdehyde condensation product (as in United States Letters Patent No.2,191,802) and the reaction between ketone-aldehyde condensationproducts, a phenol, an aldehyde and a catalyst.

As many apparently widely different embodiments of this invention maybemade without departing from the spirit thereof, it is to be understoodthat the invention. is not limited to the specific illustrative examplescontained in this specification, but rather that it encompasses thegeneralized procedures as broadly set forth, inasmuch as the detailsandmodifications are rather self evident and amendable to orthodoxchemical engineering practices.

I claim: v

1. Resinoids comprising the reaction product. carried to a point shortof gelation, between a hetone-aldehyde and a potentially reactivephenol-aldehyde condensation product, said ketone-aldehyde condensationproduct being used in the proportion of between 50 and on the combinedweights of said condensation products and selected from the classconsisting of fusible. soluble, low molecular weight substantiallynonvolatile condensation products capable of yielding distillable andcrystallizable acetylation products capable ofcondensation in thepresence of sodium hydroxide to readily yield a high molecular weightinsoluble and infusible material and produced byreactinga ketone havingthe general formula CH3-COR', wherein R represents an unsubstitutedaliphatic radical having-from one to four carbon atoms, with an aldehydehaving the general formula R'f-CHO, wherein R." represents a memberselected from the group consisting of hydrogen and unsubstitutedaliphatic radicals having from one to four carbon atoms, said reactionbetween said ketone and said aldehyde being carried out in the presenceof an alkaline catalyst until substantially all the aldehyde isconsumed, an acidic catalyst being then added to effect further reactionwhile maintaining acid conditions.

2. Resinoids comprising the reaction product, carried to a point shortof gelation, between a ketone-aldehyde and a potentially reactivephenol-aldehyde condensation product, said ketone-aldehyde condensationproduct being used in the proportion of between 50 and 95% on thecombined weights of said condensation products and selected from theclass consisting of fusible, soluble, low molecular Weight substantiallynonvolatile condensation products capable of yielding distillable andcrystallizable acetylation products apable of condensation in thepresence Q sqdiu hyd xide o. rea i e d a h m lat-W ht; insoluble, andinfusible material and produced by reacting; acetone with formaldehyde,:saidreac en betw n sai aceton n sai f maldehyde being carried out inthe presence of catalyst until substantially all the formaldehyde isconsumed, an acidic catalyst being then added, to effect. furtherreaotion while maintainflng acid conditions,

3, Resinoids comprising the, reaction product,

carried to a, pointy short'of gelation, between a soluble, low molecularweight substantially nonvolatile, condensation products capable ofyielding distillable and crystallizable acetylation productscapable ofeondensation the presence of m hydroxi e e read ly el a igh m ecusbt nseti and in u ible material n 1d. by reaet naa s ren h rms h s nula,CHZi-eCQ-rRi, wherein R} repreunsubstituted aliphatic radical having eto four carbon atoms, with an aldehyde h ving; the general formula R,V--,-CI- IO, wherein represents a member selected from the groupconsisting of hydrogen and unsubstituted alimpliatictradicals havingfrom one to four carbon atoms, said reaction between said ketone and,said aldehyde being carried out, in the presence of an alkalinecatalyst until substantially all the aldehydeis consumed, an acidiccatalyst being then added to effect further reaction whilemaintaining-acid conditions.

4, Besinoids comprising the reaction product, carried to a point shortof gelation, between a betcha-aldehyde and a potentially reactivephenol-formaldehyde condensation product, said ketone-aldehydecondensation product being used in the proportion of between 50 and 95%on the combined weights of said condensation products and selected fromthe class consisting of fusible,

soluble, low molecular weight substantially nonbeing then added toeffect further reaction while maintaining acid conditions.

.'.5..R,esinoids comprising the reaction product, carried to a pointshort of gelation, between a ketone-aldchyde and a potentially reactivephenol-aldehyde condensation product, said hetone-aldehyde condensationproduct being used in the proportion of between 70 and 90% on thecombined weights of said condensation products andselected from theclass consisting of fusible, soluble, low molecular weightsubstantiallynonvolatile condensation products capable of yieldingdistillable and crystallizable acetylation productsjcapable ofcondensation in the presence of sodium hydroxide to readily yield a highmoleculary'veightinsoluble and infusible material and produced byreacting a ketone having the generalj formula CH3CO--R, wherein Rrepresents an unsubstituted aliphatic radical having soluble, lowmolecular weight substantially Produ ed br' e ctinsacetone w h for aidei n ine o r a n a e s wit an, alde- ,toneealdehyde condensation product,being used the proportion of between 70. and o combined weights, ofsaid, condensation pro and selected from the class consisting of fuvolatile condensation productsfcapabl offy i s di til ble. nd q stalizabl acety n uc s c pab e o con en a 'on in th "a ia ef cdiu hydroxideis readilr ie da i a wei t inseluble a nfusib e mater a cad saidreactionbetween said acetone and said aldehyde being carried out in thepresenee of nal c al t unt l su ta all all he formaldehyde is consumed,an acidic catalyst, eing then added to effect further reaction; wh lemaintaining acid conditions. i

7. Resinoids comprising the reaction product, carried to a point shortof gelation, between a ketone-aldehyde and a potentially reac ivephenol-formaldehyde condensation product Said ketone-aldehydecondensation product being used in the proportion of between 70 and 30%,on-the combined weights of said condensation products and selected fromthe class consisting of fusible, soluble, low molecular weightsubstantially. nonvolatile oondensation products capable ofyieldingdistillable and crystallizable acetylattion products capableofcondensation in the presence of sodium hydroxide to readily yield a highmolecular weight insoluble and infusible material and produced byreacting a ketone havingithe general formula CH3,-CO-R', wherein R'-represents an unsubstituted aliphatic radical having from one to fourcarbon atoms, with an aldehyde having the general formula R.-.CI-I'Cwherein R, represents a member selected from the group consisting ofhydrogen and unsubstituted aliphatic radicals having from one to fourcarbon atoms, said reaction between said ketone and said aldehyde beingcarried out in the pres ence of an alkaline catalyst until substantiallall the aldehyde is consumed, an acid c cata yst being then added toeffect further reaction while maintaini ac d; ce diti ns- 8. Res no dscom r sin the rea tion. cr que carried to pq ntsbqrt i sciatica be Wee aketone-aldehyde and a potentially reactive phenol-formaldehydecondensation product, said ketone-aldehyde condensation product beingused in the proportion of between '70 and 90% on the combined weights ofsaid condensation products and selected from the class consisting offusible, soluble, low molecular weight substantially nonvolatilecondensation products capable of yielding distillable and crystallizableacetylation products capable of condensation in the presence of sodiumhydroxide to readily yield a high molecular weight insoluble andinfusible material and produced by reacting acetone with formaldehyde,said reaction between said acetone and said formaldehyde being carriedout in the presence of an alkaline catalyst until substantially all theformaldehyde is consumed, an acidic catalyst .being then added to eifectfurther reaction while maintaining acid conditions.

9. The process of producing resinoids which entails reacting a ketonealdehyde condensation product with a potentially reactivephenol-aldehyde condensation product short of the gel point,

said ketone-aldehyde condensation product being used in the proportionof between 50 and 95% 'on the combined weights of said condensation v inR represents an unsubstituted aliphatic radical having from one to fourcarbon atoms, with an aldehyde having the general formula R"CHO, whereinR represents a member selected from the group consisting of hydrogen andunsubstituted aliphatic radicals having from one to four carbon atoms,said reaction between said ketone and said aldehyde being carried out inthe presence of an alkaline catalyst until substantially all thealdehyde is consumed, an acidic catalyst being then added to effectfurther reaction while maintaining acid conditions.

10. The process of producing resinoids which entails reacting aketone-aldehyde condensation product with a potentially reactivephenol-aldehyde condensation product short of the gel point, saidketone-aldehyde condensation product being used in the proportion ofbetween 50 and 95% on the combined weights of said condensation Lproducts and selected from the class consisting 'of fusible, soluble,low molecular weight substantially non-volatile condensation productscapable of yielding distillable and crystallizable acetylation productscapable of condensation in the presence of sodium hydroxide to readilyyield a high molecular weight insoluble and infusible material andproduced by reacting acetone with formaldehyde, said reaction betweensaid acetone and said formaldehyde being carried out in the presence ofan alkaline catalyst until substantially all the formaldehyde isconsumed, an acidic catalyst being then added to effect further reactionwhile maintaining acid conditions.

point, said ketone-aldehyde condensation product being used in theproportion of between 50 and 95% on the combined weights of saidcondensation products and selected from the class consisting of fusible,soluble, low molecular weight substantially non-volatile condensationproducts capable of yielding distillable and crystallizable acetylationproducts capable of condensation in the presence of sodium hydroxide toreadily yield a high molecular weight insoluble and infusible materialand produced by reacting a ketone having the general formula CH3COR,wherein R' represents an unsubstituted aliphatic radical having from oneto four carbon atoms, with an aldehyde having the general formula R-CHO,wherein R" represents a member selected from the group consisting ofhydrogen and unsubstituted aliphatic radicals having from one to fourcarbon atoms, said reaction between said ketone and said aldehyde beingcarried out in the presence of an alkaline catalyst until substantiallyall the aldehyde is consumed, an acidic catalyst being then added toeffect further reaction while maintaining acid conditions.

12. The process of producing resinoids which entails reacting aketone-aldehyde condensation product with a potentially reactivephenol-formaldehyde condensation product short of the gel point, saidketone-aldehyde condensation product being used in the proportion ofbetween 50 and 95% on the combined weights of said condensation productsand selected from the class consisting of fusible, soluble, lowmolecular weight substantially non-volatile condensation productscapable of yielding distillable and crystallizable acetylation productscapable of condensation in the presence of sodium hydroxide to readilyyield a high molecular Weight insoluble and infusible material andproduced by reacting acetone with formaldehyde, said reaction betweensaid acetone and said formaldehyde being carried out in the presence ofan alkaline catalyst until substantially all the formaldehyde isconsumed, an acidic catalyst being then added to eifect further reactionwhile maintaining acid conditions.

GEORGE KARL VOGELSANG.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 1,514,508 Ellis Nov. 4, 19242,191,802 Novotny et a1. Feb. 27, 1940 2,206,906 Loos July 9, 19402,426,128 Trowell Aug. 19, 1947 2,545,559 Schrimpe Mar. 20, 1951 OTHERREFERENCES Kropa: Thermosetting Vinyl Polymers,

Trans. of the Electrochemical Society, pages .247, 252-257, vol. (1947).

1. RESINOIDS COMPRISING THE REACTION PRODUCT, CARRIED TO A POINT SHORTOF GELATION, BETWEEN A KETONE-ALDEHYDE AND A POTENTIALLY REACTIVEPHENOL-ALDEHYDE CONDENSATION PRODUCT, SAID KETONE-ALDEHYDE CONDENSATIONPRODUCT BEING USED IN THE PROPORTION OF BETWEEN 50 AND 95% ON THECOMBINED WEIGHTS OF SAID CONDENSATION PRODUCTS AND SELECTED FROM THECLASS CONSISTING OF FUSIBLE, SOLUBLE, LOW MOLECULAR WEIGHT SUBSTANITALLYNONVOLATILE CONDENSATION PRODUCTS CAPABLE OF YIELDING DISTILLABLE ANDCRYSTALLIZABLE ACETYLATION PRODUCTS CAPABLE OF CONDENSATION IN THEPRESENCE OF SODIUM HYDROXIDE TO READILY YIELD A HIGH MOLECULAR WEIGHTINSOLUBLE AND INFUSIBLE MATERIAL AND PRODUCEED BY REACTING A KETONEHAVING THE GENERAL FORMULA CH3-CO-R'', WHEREIN R'' REPRESENTES ANUNSUBSTITUTED ALIPHATIC RADICAL HAVING FROM ONE TO FOUR CARBON ATOMS,WITH AN ALDEHYDE HAVING THE GENERAL FORMULA R" -CHO, WHEREIN R"REPRESENTS A MEMBER SELECTED FORM THE GROUP CONSISTING OF HYDROGEN ANDUNSUBSTITUTED ALIPHATIC RADICALS HAVING FROM ONE TO FOUR CARBON ATOMS,SAID REACTION BETWEEN SAID KETONE AND SAID ALDEHYDE BEING CARRIED OUT INTHE PRESENCE OF AN ALKALINE CATALYST UNTIL SUBSTANTIALLY ALL THEALDEHYDE IS CONSUMED, AN ACIDIC CATALYST BEING THEN ADDED TO EFFECTFURTHER REACTION WHILE MAINTAINING ACID CONDITIONS.